EP1196469B1 - Condensation cross-linking polyurethane materials containing special aminosilanes, a method for the production thereof and their use - Google Patents

Condensation cross-linking polyurethane materials containing special aminosilanes, a method for the production thereof and their use Download PDF

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Publication number
EP1196469B1
EP1196469B1 EP00943797A EP00943797A EP1196469B1 EP 1196469 B1 EP1196469 B1 EP 1196469B1 EP 00943797 A EP00943797 A EP 00943797A EP 00943797 A EP00943797 A EP 00943797A EP 1196469 B1 EP1196469 B1 EP 1196469B1
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EP
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Prior art keywords
general formula
polyurethane
carbon atoms
component
polyurethane compositions
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EP00943797A
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German (de)
French (fr)
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EP1196469A2 (en
Inventor
Ulrich Walter
Lutz Schmalstieg
Ralf Lemmerz
Oswald Wilmes
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Bayer AG
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Bayer AG
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Priority claimed from DE1999129011 external-priority patent/DE19929011A1/en
Priority claimed from DE19929029A external-priority patent/DE19929029A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/83—Chemically modified polymers
    • C08G18/837—Chemically modified polymers by silicon containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2190/00—Compositions for sealing or packing joints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3462—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/04—Non-macromolecular organic compounds
    • C09K2200/0494—Silicon-containing compounds

Definitions

  • the invention relates to polyurethane compositions which crosslink via a silane polycondensation, containing at least one alkoxysilane-functional polyurethane, at least a basic filler, at least one reaction product of an aminosilane with a maleic or fumaric acid ester, at least one organometallic compound and, if appropriate, other auxiliaries, a process for their preparation and their use.
  • An overview article on The topic can be found in "Adhesives Age” 4/1995, page 30 ff. (Authors: Ta-Min Feng, B.A. Waldmann).
  • Such alkoxysilane-terminated, moisture-curing One-component polyurethanes are increasingly considered to be flexible Coating, sealing and adhesive compositions in construction and in the automotive industry used. These applications place high demands on the Elasticity, adhesiveness and the curing speed.
  • the object of the present invention was therefore to contain aminosilanes to provide a silane polycondensation crosslinking polyurethane compositions which have improved storage stability.
  • the invention is based on the surprising observation that instead of Aminosilanes usually used as adhesion promoters are used according to the invention Improved adducts of aminosilanes with maleic or fumaric acid esters mechanical properties and improved storage stability.
  • reaction products to be used according to the invention as component C) Maleic or fumaric acid esters and aminosilanes are known in principle and will be described by way of example in EP-A 596360 or EP-A 831108. According to the These publications teach the implementation products of painting or Fumaric acid esters with aminosilanes used for reaction with isocyanate prepolymers. The use of these products as an additive to improve mechanical Properties and to improve the adhesion of over silane polycondensation crosslinking polyurethanes are not yet known.
  • polyurethanes containing alkoxysilane end groups to be used according to the invention as component A) are known in principle and are produced by reacting long-chain, preferably linear NCO prepolymers with amino-functional silanes of the general structural formula (II) where R 1 is an organic radical having 1 to 12 carbon atoms, preferably a phenyl group or particularly preferably a radical of the general structural formula (IIb), where R 4 is an alkyl group having 1 to 4 carbon atoms.
  • n stands for an integer from 2 to 4, preferably 3.
  • X, Y, Z in the above structural formula mean the same or different organic radicals, with the proviso that at least one of the radicals is an alkoxy group with 1 to 4 carbon atoms. Preferably at least one the residues are a methoxy or ethoxy group. X, Y and Z are particularly preferred for one methoxy group each.
  • suitable amino-functional silanes according to structural formula (I) are N-methyl-3-aminopropyltrimethoxysilane, N-methyl-3-aminopropyltriethoxysilane, N-butyl-3-aminopropyltrimethoxysilane, N-Phenyl-3-aminopropyltrimethoxysilane can preferably be used.
  • Those in EP-A can be used with particular preference 596360 described aspartic acid esters as they result from the reaction of aminosilanes of the general structural formula (II) with maleic or fumaric acid esters Formula (III) arise.
  • NCO prepolymers are prepared in a known manner by reacting Polyether polyols preferably polyether diols made with diisocyanates and have an NCO content between 0.4 and 4%.
  • Further Fillers are e.g. B. reinforcing and non-reinforcing fillers, such as. B. pyrogenic or precipitated silica, soot or quartz powder. Both the basic fillers as well as the other reinforcing or non-reinforcing fillers if necessary, be surface-modified. Are particularly preferably used as basic fillers B) precipitated or ground chalk and pyrogenic silicas. Component B) can of course also be mixtures of fillers act.
  • Examples of usable aminosilane compounds of the formula (II) are 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane and N-aminoethyl-3-aminopropylmethyldimethoxysilane.
  • R 3 represents a linear or branched aliphatic hydrocarbon radical with a maximum of 12 carbon atoms.
  • suitable maleic or fumaric acid esters are maleic acid diethyl ester, maleic acid dimethyl ester, maleic acid dibutyl ester, maleic acid dioctyl ester, fumaric acid diethyl ester, fumaric acid dimethyl ester, fumaric acid dioctyl ester.
  • All organometallic catalysts can be used as component E) which are known to promote silane polycondensation. These are connections in particular of tin and titanium.
  • Preferred tin compounds are, for example Dibutyltin dilaurate, dibutyltin diacetate and dioctyltin maleate, Tin (II) octoate or dibutyltin bis-acetoacetonate.
  • Preferred titanium compounds are, for example, alkyl titanates such as tetraisopropyl titanate, tetrabutyl titanate and chelated titanium compounds such as ethyl diisobutyl bisacetoacetate titanate. Dibutyltin bis-acetoacetonate is particularly preferably used as component E).
  • Additives and auxiliary substances F) within the meaning of the invention may be mentioned: desiccants, Plasticizers, adhesives other than those mentioned under C), thixotropic agents, Light stabilizers, pigments and protective agents, e.g. Fungicides.
  • Alkoxysilyl compounds such as vinyltrimethoxysilane may be mentioned as drying agents, Methyltrimethoxysilane, i-butyltrimethoxysilane, hexadecyltrimethoxysilane.
  • plasticizers are phthalic acid esters, adipic acid esters, Called alkyl sulfonic acid ester of phenol or phosphoric acid ester.
  • a thixotropic agent examples include polyamides, hydrogenated castor oil secondary products or Called polyvinyl chloride.
  • adhesion promoters in addition to those under C) mentioned compounds aminosilanes of the known type, epoxysilanes and / or Mercaptosilanes are used.
  • the polyurethane compositions according to the invention preferably consist of 30 to 80% by weight of component A), 10 to 50% by weight of component B), 0.5 to 3% by weight of component C), 0.02 to 1% by weight of component E) and 0 to 40% by weight of component F).
  • the present invention also relates to a method for producing the Condensation-crosslinking polyurethane compositions according to the invention.
  • Components A), B), E) and optionally F) are with the exclusion of Moisture mixed and then mixed with component C).
  • the Component C) which can be used according to the invention is generated in situ.
  • the present invention also relates to the use of the invention reaction components of aminosilanes and which can be used as component C) Maleic and fumaric acid esters as an additive in condensation-crosslinking polyurethane compositions.
  • the present invention furthermore relates to the use of the invention condensation-crosslinking polyurethane materials as sealant, adhesive or Coating material.
  • condensation-crosslinking polyurethane compositions according to the invention show on the one hand, rapid curing with skin formation times between 15 and 120 Minutes, but on the other hand have excellent storage stability in the temperature range up to 60 ° C.
  • the crosslinked polymers in particular show improved mechanical properties an improved elongation at break compared to analog systems, the conventional Contain aminosilanes.
  • the invention Polyurethane compositions through excellent adhesion, especially wet adhesion on all conceivable substrates such as metal, ceramic, plastic, stone or Concrete.
  • the mixture is dispersed for 10 minutes at a pressure of 100 mbar, the internal temperature rising to 60 ° C. Then be 1.5 parts by weight N-aminoethyl-3-aminopropyltrimethoxysilane added and incorporated at a pressure of 100 mbar by stirring for 10 minutes.
  • the sealant produced in this way shows excellent stability, adheres to almost all substrates and hardens with a skin formation time of 30 minutes.
  • the product is filled into a commercially available cartridge and stored at 50 ° C. After a storage period of 90 days, the product can still be processed without any problems and shows unchanged product properties.
  • the mixture is dispersed for 10 minutes at a pressure of 100 mbar, the internal temperature rising to 60 ° C. Then 2.1 parts by weight N-aminoethyl-3-aminopropyltrimethoxysilane added and incorporated at a pressure of 100 mbar by stirring for 10 minutes.
  • the sealant produced in this way shows excellent stability and adheres almost all substrates and hardens with a skin formation time of 40 minutes out.
  • the product is filled into a commercially available cartridge and stored at 50 ° C. After a storage period of 90 days, the product can still be processed without any problems and shows unchanged product properties.
  • Example 1 is repeated, with the change that no maleic acid diethyl ester is added becomes.
  • the product is filled into a commercially available cartridge and at 50 ° C stored. After a storage period of 60 days, the product can no longer be used squeeze the cartridge and is gelled.
  • Example 2 is repeated with the change that no dimethyl maleate is added.
  • the product is filled into a commercially available cartridge and included in the Stored at 50 ° C. After a storage period of 35 days, the product cannot be Squeeze more out of the cartridge and is gelled.
  • the mixture is dispersed for 10 minutes at a pressure of 100 mbar, the internal temperature rising to 60 ° C. Then be 2.5 parts by weight Diethyl N- (3-trimethoxysilylpropyl) aspartate (prepared according to EP-A 596 360, Ex. 5) added and incorporated at a pressure of 100 mbar by stirring for 10 minutes.
  • the sealant produced in this way shows excellent stability and adheres almost all substrates and hardens with a skin formation time of 50 minutes out.
  • the product is filled into a commercially available cartridge and stored at 50 ° C. After a storage period of 90 days, the product can still be processed without any problems and shows unchanged product properties.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Sealing Material Composition (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Paints Or Removers (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Silicon Polymers (AREA)

Abstract

This invention relates to polyurethane compositions which cross-link via a silane polycondensation and contain at least one alkoxysilane-functional polyurethane, at least one basic filler, at least one reaction product of an aminosilane with a maleic or fumaric ester, at least one organometallic compound and optionally additional auxiliary substances, to a process for their preparation, and to their use.

Description

Die Erfindung betrifft über eine Silanpolykondensation vernetzende Polyurethanmassen, enthaltend mindestens ein alkoxysilanfunktionelles Polyurethan, mindestens einen basischen Füllstoff, mindestens ein Umsetzungsprodukt eines Aminosilans mit einem Malein- oder Fumarsäureester, mindestens eine metallorganische Verbindung und ggf. weitere Hilfsstoffe, ein Verfahren zu deren Herstellung sowie deren Verwendung.The invention relates to polyurethane compositions which crosslink via a silane polycondensation, containing at least one alkoxysilane-functional polyurethane, at least a basic filler, at least one reaction product of an aminosilane with a maleic or fumaric acid ester, at least one organometallic compound and, if appropriate, other auxiliaries, a process for their preparation and their use.

Alkoxysilanfunktionelle Polyurethane, die über eine Silanpolykondensation vernetzen, gehören zum lange bekannten Stand der Technik. Ein Übersichtsartikel zur Thematik findet sich in "Adhesives Age" 4/1995, Seite 30 ff. (Autoren: Ta-Min Feng, B. A. Waldmann). Derartige Alkoxysilan-terminierte, feuchtigkeitshärtende Einkomponenten-Polyurethane werden in zunehmendem Maße als weichelastische Beschichtungs-, Dichtungs- und Klebemassen im Bauwesen und in der Automobilindustrie verwendet. Bei diesen Anwendungen werden hohe Anforderungen an das Dehn-, Adhäsionsvermögen und an die Aushärtegeschwindigkeit gestellt.Alkoxysilane-functional polyurethanes that crosslink via silane polycondensation, belong to the long known state of the art. An overview article on The topic can be found in "Adhesives Age" 4/1995, page 30 ff. (Authors: Ta-Min Feng, B.A. Waldmann). Such alkoxysilane-terminated, moisture-curing One-component polyurethanes are increasingly considered to be flexible Coating, sealing and adhesive compositions in construction and in the automotive industry used. These applications place high demands on the Elasticity, adhesiveness and the curing speed.

Beispielhaft werden derartige Produkte beschrieben in der EP-A-596360, EP-A 831108, der EP-A 807649 oder der EP-A 676403. Bei der Formulierung derartiger Systeme werden typischerweise metallorganische Katalysatoren sowie Haftvermittler vom Aminosilan-Typ mitverwendet. Durch den Zusatz der Aminosilanverbindungen kann es aber oftmals zu Lagerstabilitätsproblemen kommen, insbesondere dann, wenn höhere Anteile an Aminosilanen eingesetzt werden, um eine gute Haftung auf problematischen Untergründen zu erzielen.Such products are described by way of example in EP-A-596360, EP-A 831108, EP-A 807649 or EP-A 676403. In the formulation of such Systems typically become organometallic catalysts and adhesion promoters of the aminosilane type. By adding the aminosilane compounds But there can often be problems with storage stability, especially if if higher proportions of aminosilanes are used to ensure good adhesion to achieve problematic substrates.

Aufgabe der vorliegenden Erfindung war es daher, Aminosilane enthaltende, über eine Silanpolykondensation vemetzende Polyurethanmassen bereitzustellen, die eine verbesserte Lagerstabilität aufweisen. The object of the present invention was therefore to contain aminosilanes to provide a silane polycondensation crosslinking polyurethane compositions which have improved storage stability.

Diese Aufgabe konnte mit der Bereitstellung der nachstehend näher beschriebenen kondensationsvernetzenden Polyurethanmassen gelöst werden.This task could be accomplished with the provision of those detailed below condensation-crosslinking polyurethane compositions are solved.

Gegenstand der Erfindung sind über eine Silanpolykondensation vernetzende Polyurethanmassen, enthaltend

  • A) mindestens ein alkoxysilanfunktionelles Polyurethan mit Endgruppen der allgemeinen Formel (I)
    Figure 00020001
       in welcher
    R1
    für einen organischen Rest mit 1 bis 12 Kohlenstoffatomen,
    n
    für eine ganze Zahl von 2 bis 4 steht
    und
    X,Y,Z
    gleiche oder verschiedene organische Reste darstellen, mit der Maßgabe, daß mindestens einer der Reste eine Alkoxygruppe mit 1 bis 4 Kohlenstoffatomen, vorzugsweise eine Methoxy- oder Ethoxygruppe darstellt,
  • B) mindestens einen basischen Füllstoff,
  • C) mindestens ein Umsetzungsprodukt aus mindestens einem Aminosilan der allgemeinen Formel (II)
    Figure 00030001
       in welcher
    R2
    für ein Wasserstoffatom, oder eine Aminoethylgruppe steht und
    n, X,Y,Z
    die bei Formel (I)genannte Bedeutung haben,
       mit mindestens einem Malein- oder Fumarsäure(ester) der allgemeinen Formel (III) R3OOC-CH=CH-COOR3    in welcher
       R3 für eine Alkylgruppe mit 1 bis 12 Kohlenstoffatomen steht,
  • E) mindestens eine metallorganische Verbindung und
  • F) ggf. weitere Hilfsstoffe.
    • The invention relates to polyurethane compositions which crosslink via a silane polycondensation, comprising
  • A) at least one alkoxysilane-functional polyurethane with end groups of the general formula (I)
    Figure 00020001
    in which
    R 1
    for an organic radical with 1 to 12 carbon atoms,
    n
    represents an integer from 2 to 4
    and
    X, Y, Z
    represent identical or different organic radicals, with the proviso that at least one of the radicals represents an alkoxy group with 1 to 4 carbon atoms, preferably a methoxy or ethoxy group,
  • B) at least one basic filler,
  • C) at least one reaction product from at least one aminosilane of the general formula (II)
    Figure 00030001
    in which
    R 2
    represents a hydrogen atom or an aminoethyl group and
    n, X, Y, Z
    have the meaning given for formula (I),
    with at least one maleic or fumaric acid (ester) of the general formula (III) R 3 OOC-CH = CH-COOR 3 in which
    R 3 represents an alkyl group with 1 to 12 carbon atoms,
  • E) at least one organometallic compound and
  • F) if necessary, other auxiliaries.

    • Der Erfindung liegt die überraschende Beobachtung zugrunde, daß die anstelle der üblicherweise als Haftvermittler eingesetzten Aminosilane erfindungsgemäß eingesetzten Addukte von Aminosilanen mit Malein- oder Fumarsäureestern verbesserte mechanische Eigenschaften und eine verbesserte Lagerstabilität bewirken.The invention is based on the surprising observation that instead of Aminosilanes usually used as adhesion promoters are used according to the invention Improved adducts of aminosilanes with maleic or fumaric acid esters mechanical properties and improved storage stability.

    Die erfindungsgemäß als Komponente C) einzusetzenden Umsetzungsprodukte aus Malein- bzw. Fumarsäureestern und Aminosilanen sind prinzipiell bekannt und werden beispielhaft beschrieben in der EP-A 596360 oder der EP-A 831108. Gemäß der Lehre dieser Veröffentlichungen werden die Umsetzungsprodukte von Malein- bzw. Fumarsäureestern mit Aminosilanen zur Umsetzung mit Isocyanatprepolymeren eingesetzt. Die Verwendung dieser Produkte als Additiv zur Verbesserung der mechanischen Eigenschaften und zur Verbesserung der Haftung von über Silanpolykondensation vernetzenden Polyurethanen ist bisher nicht bekannt.The reaction products to be used according to the invention as component C) Maleic or fumaric acid esters and aminosilanes are known in principle and will be described by way of example in EP-A 596360 or EP-A 831108. According to the These publications teach the implementation products of painting or Fumaric acid esters with aminosilanes used for reaction with isocyanate prepolymers. The use of these products as an additive to improve mechanical Properties and to improve the adhesion of over silane polycondensation crosslinking polyurethanes are not yet known.

    Die als Komponente A) erfindungsgemäß einzusetzenden Alkoxysilan-Endgruppen aufweisenden Polyurethane sind prinzipiell bekannt und werden hergestellt durch Umsetzung langkettiger, vorzugsweise linearer NCO-Prepolymere mit aminofunktionellen Silanen der allgemeinen Strukturformel (II)

    Figure 00040001
    wobei R1 für einen organischen Rest mit 1 bis 12 Kohlenstoffatomen, vorzugsweise eine Phenylgruppe oder besonders bevorzugt einen Rest der allgemeinen Sturkturformel (IIb) steht,
    Figure 00040002
    wobei R4 eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen steht. In der obengenannten Strukturformel steht n für eine ganze Zahl von 2 bis 4, vorzugsweise 3.The polyurethanes containing alkoxysilane end groups to be used according to the invention as component A) are known in principle and are produced by reacting long-chain, preferably linear NCO prepolymers with amino-functional silanes of the general structural formula (II)
    Figure 00040001
    where R 1 is an organic radical having 1 to 12 carbon atoms, preferably a phenyl group or particularly preferably a radical of the general structural formula (IIb),
    Figure 00040002
    where R 4 is an alkyl group having 1 to 4 carbon atoms. In the structural formula mentioned above, n stands for an integer from 2 to 4, preferably 3.

    X, Y, Z bedeuten in der obengenannten Strukturformel gleiche oder verschiedene organische Reste, mit der Maßgabe, daß mindestens einer der Reste eine Alkoxygruppe mit 1 bis 4 Kohlenstoffatomen darstellt. Vorzugsweise ist mindestens einer der Reste eine Methoxy- oder Ethoxygruppe. Besonders bevorzugt steht X, Y und Z für jeweils eine Methoxygruppe.X, Y, Z in the above structural formula mean the same or different organic radicals, with the proviso that at least one of the radicals is an alkoxy group with 1 to 4 carbon atoms. Preferably at least one the residues are a methoxy or ethoxy group. X, Y and Z are particularly preferred for one methoxy group each.

    Beispiele für geeignete arninofunktionelle Silane gemäß Strukturformel (I) sind N-Methyl-3-aminopropyltrimethoxysilan, N-Methyl-3-aminopropyltriethoxysilan, N-Butyl-3-aminopropyltrimethoxysilan, Vorzugsweise einsetzbar ist N-Phenyl-3-aminopropyltrimethoxysilan. Besonders bevorzugt einsetzbar sind die in der EP-A 596360 beschriebenen Asparaginsäureester wie sie durch Umsetzung von Aminosilanen der allgemeinen Strukturformel (II) mit Malein- oder Fumarsäureestern der Formel (III) entstehen.Examples of suitable amino-functional silanes according to structural formula (I) are N-methyl-3-aminopropyltrimethoxysilane, N-methyl-3-aminopropyltriethoxysilane, N-butyl-3-aminopropyltrimethoxysilane, N-Phenyl-3-aminopropyltrimethoxysilane can preferably be used. Those in EP-A can be used with particular preference 596360 described aspartic acid esters as they result from the reaction of aminosilanes of the general structural formula (II) with maleic or fumaric acid esters Formula (III) arise.

    Zur Herstellung der Alkoxysilan-Endgruppen aufweisenden Polyurethane A) einsetzbare NCO-Prepolymere werden in bekannter Weise durch Umsetzung von Polyetherpolyolen vorzugsweise Polyetherdiolen mit Diisocyanaten hergestellt und weisen einen NCO-Gehalt zwischen 0,4 und 4 % auf.Usable for the preparation of the polyurethanes A) having alkoxysilane end groups NCO prepolymers are prepared in a known manner by reacting Polyether polyols preferably polyether diols made with diisocyanates and have an NCO content between 0.4 and 4%.

    Als basische Füllstoffe B) einsetzbar sind gefällte oder gemahlene Kreiden, Metalloxide, -sulfate, -silicate, -hydroxyde, -carbonate und -hydrogencarbonate. Weitere Füllstoffe sind z. B. verstärkende und nichtverstärkende Füllstoffe, wie z. B. pyrogene oder gefällte Kieselsäuren, Ruß oder Quarzmehl. Sowohl die basischen Füllstoffe als auch die weiteren verstärkenden oder nichtverstärkenden Füllstoffe können gegebenenfalls oberflächen-modifiziert sein. Besonders bevorzugt einsetzbar sind als basische Füllstoffe B) gefällte oder gemahlene Kreiden sowie pyrogene Kieselsäuren. Bei der Komponente B) kann es sich selbstverständlich auch um Gemische von Füllstoffen handeln.Precipitated or ground chalk, metal oxides, sulfates, silicates, hydroxides, carbonates and bicarbonates. Further Fillers are e.g. B. reinforcing and non-reinforcing fillers, such as. B. pyrogenic or precipitated silica, soot or quartz powder. Both the basic fillers as well as the other reinforcing or non-reinforcing fillers if necessary, be surface-modified. Are particularly preferably used as basic fillers B) precipitated or ground chalk and pyrogenic silicas. Component B) can of course also be mixtures of fillers act.

    Als Komponente C) werden Umsetzungsprodukte von Aminosilanverbindungen der allgemeinen Strukturformel (II)

    Figure 00060001
       in welcher
    R2, X, Y, Z und n die oben angegebene Bedeutung haten,
    mit Malein- oder Fumarsäure(estern) der allgemeinen Formel (III) R3OOC-CH=CH-COOR3 in welcher

    R3
    für eine Alkylgruppe mit 1 bis 12 Kohlenstoffatomen steht,
    eingesetzt.As component C) reaction products of aminosilane compounds of the general structural formula (II)
    Figure 00060001
    in which
    R 2 , X, Y, Z and n had the meaning given above,
    with maleic or fumaric acid (esters) of the general formula (III) R 3 OOC-CH = CH-COOR 3 in which
    R 3
    represents an alkyl group with 1 to 12 carbon atoms,
    used.

    Beispiele für einsetzbare Aminosilanverbindungen der Formel (II) sind 3-Aminopropyltrimethoxysilan, 3-Aminopropyltriethoxysilan, N-Aminoethyl-3-aminopropyltrimethoxysilan, N-Aminoethyl-3-aminopropyltriethoxysilan, 3-Aminopropyl-methyldiethoxysilan und N-Aminoethyl-3-aminopropylmethyldimethoxysilan.Examples of usable aminosilane compounds of the formula (II) are 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane and N-aminoethyl-3-aminopropylmethyldimethoxysilane.

    In der Formel (III) steht R3 für einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit maximal 12 Kohlenstoffatomen. Beispiele für geeignete Malein- bzw. Fumarsäureester sind Maleinsäurediethylester, Maleinsäuredimethylester, Maleinsäuredibutylester, Maleinsäuredioctylester, Fumarsäurediethylester, Fumarsäuredimethylester, Fumarsäuredioctylester. In formula (III), R 3 represents a linear or branched aliphatic hydrocarbon radical with a maximum of 12 carbon atoms. Examples of suitable maleic or fumaric acid esters are maleic acid diethyl ester, maleic acid dimethyl ester, maleic acid dibutyl ester, maleic acid dioctyl ester, fumaric acid diethyl ester, fumaric acid dimethyl ester, fumaric acid dioctyl ester.

    Für den Fall, daß als Aminosilane Produkte eingesetzt werden in denen gemäß Formel (II) R2 ein Wasserstoffatom bedeutet, entstehen bei der Umsetzung mit den Malein- bzw. Fumarsäureestern gemäß der Lehre der EP-A 596360 Asparaginsäureester der allgemeinen Strukturformel (IV)

    Figure 00070001
    in welcher
    R3, X, Y, Z und n die bei den Formeln (II) und (III) angegebene Bedeutung haben.In the event that products are used as aminosilanes in which R 2 is a hydrogen atom according to formula (II), reaction with the maleic or fumaric acid esters according to the teaching of EP-A 596360 results in aspartic acid esters of the general structural formula (IV)
    Figure 00070001
    in which
    R 3 , X, Y, Z and n have the meaning given for the formulas (II) and (III).

    Für den besonders bevorzugten Fall, daß als Aminosilane der Formel (II) Produkte eingesetzt werden, in denen R2 eine Aminoethylgruppe bedeutet, entstehen durch Cyclokondensationsreaktion Piperazinonderivate der allgemeinen Formel (V)

    Figure 00070002
    in welcher
    R3, X, Y, Z und n die bei Formel (IV) angegebene Bedeutung haben. In the particularly preferred case that products in which R 2 represents an aminoethyl group are used as aminosilanes of the formula (II), piperazinone derivatives of the general formula (V) are formed by the cyclocondensation reaction
    Figure 00070002
    in which
    R 3 , X, Y, Z and n have the meaning given for formula (IV).

    Als Komponente E) können alle metallorganischen Katalysatoren eingesetzt werden, die bekanntermaßen die Silanpolykondensation fördern. Dies sind insbesondere Verbindungen des Zinns und des Titans. Bevorzugte Zinnverbindungen sind beispielsweise Dibutylzinndilaurat, Dibutylzinndiacetat und Dioctylzinnmaleat, Zinn(II)octoat oder Dibutylzinn-bis-acetoacetonat. Bevorzugte Titanverbindungen sind beispielsweise Alkyltitanate, wie Tetraisopropyltitanat, Tetrabutyltitanat und chelatisierte Titanverbindungen, wie Diisobutyl-bisacetessigsäureethylester-titanat. Besonders bevorzugt wird Dibutylzinn-bis-acetoacetonat als Komponente E) eingesetzt.All organometallic catalysts can be used as component E) which are known to promote silane polycondensation. These are connections in particular of tin and titanium. Preferred tin compounds are, for example Dibutyltin dilaurate, dibutyltin diacetate and dioctyltin maleate, Tin (II) octoate or dibutyltin bis-acetoacetonate. Preferred titanium compounds are, for example, alkyl titanates such as tetraisopropyl titanate, tetrabutyl titanate and chelated titanium compounds such as ethyl diisobutyl bisacetoacetate titanate. Dibutyltin bis-acetoacetonate is particularly preferably used as component E).

    Zusätze und Hilfsstoffe F) im Sinne der Erfindung seien genannt: Trockenmittel, Weichmacher, andere als die unter C) genannten Haftmittel, Thixotropiermittel, Lichtschutzmittel, Pigmente und Schutzmittel, z.B. Fungizide.Additives and auxiliary substances F) within the meaning of the invention may be mentioned: desiccants, Plasticizers, adhesives other than those mentioned under C), thixotropic agents, Light stabilizers, pigments and protective agents, e.g. Fungicides.

    Als Trockenmittel seien insbesondere Alkoxysilylverbindungen genannt wie Vinyltrimethoxysilan, Methyltrimethoxysilan, i-Butyltrimethoxysilan, Hexadecyltrimethoxysilan. Als Weichmacher seien beispielhaft Phtalsäureester, Adipinsäureester, Alkylsulfonsäureester des Phenols oder Phosphorsäureester genannt. Als Thixotropiermittel seien beispielhaft Polyamide, hydrierte Ricinusöl-Folgeprodukte oder auch Polyvinylchlorid genannt. Als Haftvermittler können zusätzlich zu den unter C) genannten Verbindungen Aminosilane der bekannten Art, Epoxysilane und/oder Mercaptosilane eingesetzt werden.Alkoxysilyl compounds such as vinyltrimethoxysilane may be mentioned as drying agents, Methyltrimethoxysilane, i-butyltrimethoxysilane, hexadecyltrimethoxysilane. Examples of plasticizers are phthalic acid esters, adipic acid esters, Called alkyl sulfonic acid ester of phenol or phosphoric acid ester. As a thixotropic agent Examples include polyamides, hydrogenated castor oil secondary products or Called polyvinyl chloride. As adhesion promoters in addition to those under C) mentioned compounds aminosilanes of the known type, epoxysilanes and / or Mercaptosilanes are used.

    Die erfindungsgemäßen Polyurethanmassen bestehen vorzugsweise aus 30 bis 80 Gew% an Komponente A), 10 bis 50 Gew% an Komponente B), 0,5 bis 3 Gew% an Komponente C), 0,02 bis 1 Gew% an Komponente E) sowie 0 bis 40 Gew% an Komponente F).The polyurethane compositions according to the invention preferably consist of 30 to 80% by weight of component A), 10 to 50% by weight of component B), 0.5 to 3% by weight of component C), 0.02 to 1% by weight of component E) and 0 to 40% by weight of component F).

    Gegenstand der vorliegenden Erfindung ist auch ein Verfahren zur Herstellung der erfindungsgemäßen kondensationsvernetzenden Polyurethanmassen. Beim erfindungsgemäßen Verfahrens wird die Komponente C) in einem separaten Reaktionsgefäß hergestellt, durch Umsetzung der Aminosilane mit den Malein- bzw. Fumarsäureestern analog der Lehre der EP-A 596360 im Temperaturbereich von 0 bis 100 °C. Die Komponenten A), B), E) sowie gegebenenfalls F) werden unter Ausschluß von Feuchtigkeit vermischt und anschließend mit der Komponente C) versetzt.The present invention also relates to a method for producing the Condensation-crosslinking polyurethane compositions according to the invention. In the invention Process component C) in a separate reaction vessel prepared by reacting the aminosilanes with the maleic or fumaric acid esters analogous to the teaching of EP-A 596360 in the temperature range from 0 to 100 ° C. Components A), B), E) and optionally F) are with the exclusion of Moisture mixed and then mixed with component C).

    In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird die erfindungsgemäß einsetzbare Komponente C) in situ erzeugt. Bei dieser Verfahrensweise werden die Komponenten A), B), E) sowie gegebenenfalls F) zusammen mit den zur Herstellung der Komponente C) einsetzbaren Malein- bzw. Fumarsäureestern unter Ausschluß von Feuchtigkeit vermischt und anschließend mit den erfindungsgemäß zur Herstellung der Komponente C) einsetzbaren Aminosilanen versetzt.In a preferred embodiment of the method according to the invention, the Component C) which can be used according to the invention is generated in situ. With this procedure components A), B), E) and optionally F) together with the maleic or fumaric acid esters that can be used to prepare component C) mixed in the absence of moisture and then with the invention aminosilanes which can be used to prepare component C).

    Gegenstand der vorliegenden Erfindung ist auch die Verwendung der erfindungsgemäß als Komponente C) einsetzbaren Umsetzungsprodukte von Aminosilanen und Malein- und Fumarsäureestern als Additiv in kondensationsvernetzenden Polyurethanmassen.The present invention also relates to the use of the invention reaction components of aminosilanes and which can be used as component C) Maleic and fumaric acid esters as an additive in condensation-crosslinking polyurethane compositions.

    Gegenstand der vorliegenden Erfindung ist weiterhin die Verwendung der erfindungsgemäßen kondensationsvernetzenden Polyurethanmassen als Dichtstoff, Kleboder Beschichtungsmaterial.The present invention furthermore relates to the use of the invention condensation-crosslinking polyurethane materials as sealant, adhesive or Coating material.

    Die erfindungsgemäßen kondensationsvernetzenden Polyurethanmassen zeigen einerseits eine schnelle Aushärtung mit Hautbildungszeiten zwischen 15 und 120 Minuten, besitzen aber andererseits eine hervorragende Lagerstabilität im Temperaturbereich bis zu 60°C.The condensation-crosslinking polyurethane compositions according to the invention show on the one hand, rapid curing with skin formation times between 15 and 120 Minutes, but on the other hand have excellent storage stability in the temperature range up to 60 ° C.

    Die vernetzten Polymere zeigen verbesserte mechanische Eigenschaften insbesondere eine verbesserte Reißdehnung im Vergleich zu analogen Systemen, die konventionelle Aminosilane enthalten. Außerdem zeichnen sich die erfindungsgemäßen Polyurethanmassen durch hervoragende Haftung insbesondere Naßhaftung auf allen erdenklichen Substraten wie beispielsweise Metall, Keramik, Kunststoff, Stein oder Beton aus. The crosslinked polymers in particular show improved mechanical properties an improved elongation at break compared to analog systems, the conventional Contain aminosilanes. In addition, the invention Polyurethane compositions through excellent adhesion, especially wet adhesion on all conceivable substrates such as metal, ceramic, plastic, stone or Concrete.

    BeispieleExamples Herstellung eines Alkoxysilyl-Endgruppen aufweisenden Polyurethans A1)Preparation of a Polyurethane A1 Having Alkoxysilyl End Groups

    2000 g eines Polyetherdiols der OH-Zahl 28, hergestellt durch Propoxylierung von Propylenglykol und anschließende Ethoxylierung des Propoxylierungsproduktes (PO/EO-Verhältnis = 80:20) werden mit 155,4 g Isophorondiisocyanat bei 70°C unter Zusatz von 0,02 g Dibutylzinndilaurat bis zum Erreichen des theoretischen NCO-Gehaltes von 0,78 % prepolymerisiert. Nach Abkühlen auf 60°C tropft man 140,4 g N-(3-Trimethoxysilylpropyl)asparaginsäure-diethylester (hergestellt gemäß EP-A 596 360, Bsp. 5) zügig zu und rührt, bis im IR-Spektrum keine Isocyanatbande mehr zu sehen ist. Das erhaltene Alkoxysilyl-Endgruppen aufweisende Polyurethanprepolymer hat eine Viskosität von 76000 mPas (23°C).2000 g of a polyether diol of OH number 28, prepared by propoxylation of Propylene glycol and subsequent ethoxylation of the propoxylation product (PO / EO ratio = 80:20) with 155.4 g of isophorone diisocyanate at 70 ° C with the addition of 0.02 g of dibutyltin dilaurate until the theoretical is reached NCO content of 0.78% prepolymerized. After cooling to 60 ° C, dropwise 140.4 g of diethyl N- (3-trimethoxysilylpropyl) aspartate (prepared according to EP-A 596 360, Example 5) rapidly and stirred until no isocyanate band in the IR spectrum there is more to see. The resulting polyurethane prepolymer containing alkoxysilyl end groups has a viscosity of 76000 mPas (23 ° C).

    Herstellung eines Alkoxysilyl-Endgruppen aufweisenden Polyurethans A2)Production of a Polyurethane A2 Having Alkoxysilyl End Groups

    2000 g eines Polyetherdiols der OH-Zahl 28, hergestellt durch Propoxylierung von Propylenglykol und anschließende Ethoxylierung des Propoxylierungsproduktes (PO/EO-Verhältnis = 80:20) werden mit 155,4 g Isophorondiisocyanat bei 70°C unter Zusatz von 0,02 g Dibutylzinndilaurat bis zum Erreichen des theoretischen NCO-Gehaltes von 0,78 % prepolymerisiert. Nach Abkühlen auf 60°C tropft man 102 g N-Phenyl-3-aminopropyltrimethoxysilan zügig zu und rührt, bis im IR-Spektrum keine Isocyanatbande mehr zu sehen ist. Das erhaltene Alkoxysilyl-Endgruppen aufweisende Polyurethanprepolymer hat eine Viskosität von 86000 mPas (23°C). 2000 g of a polyether diol of OH number 28, prepared by propoxylation of Propylene glycol and subsequent ethoxylation of the propoxylation product (PO / EO ratio = 80:20) with 155.4 g of isophorone diisocyanate at 70 ° C with the addition of 0.02 g of dibutyltin dilaurate until the theoretical is reached NCO content of 0.78% prepolymerized. After cooling to 60 ° C, dropwise Swiftly add 102 g of N-phenyl-3-aminopropyltrimethoxysilane and stir until in the IR spectrum no more isocyanate band can be seen. The alkoxysilyl end groups obtained The polyurethane prepolymer has a viscosity of 86000 mPas (23 ° C).

    Beispiel 1example 1 Herstellung einer erfindungsgemäßen PolyurethanmasseProduction of a polyurethane composition according to the invention

    In einem handelsüblichen Planetenmischer werden die folgenden Komponenten zu einem gebrauchsfertigen Dichtstoff verarbeitet: 36,4 Gew-Teile Polyurethan A1) 12,9 Gew.-Teile Diisoundecylphtalat (Weichmacher) 0,02 Gew.-Teile Dibutylzinn-bis-acetoacetonat (10%ig gelöst in Solvent-naphta 100) 1,50 Gew.-Teile Vinyltrimethoxysilan 46,2 Gew.-Teile Fällungskreide (Typ: Socal® U1S2) 2,00 Gew.-Teile Maleinsäurediethylester 1,40 Gew.-Teile Disparlon® NVG8403 S (Thixotropiermittel der Kusumoto Chem. Ltd.) The following components are processed into a ready-to-use sealant in a commercially available planetary mixer: 36.4 parts by weight Polyurethane A1) 12.9 parts by weight Diisoundecyl phthalate (plasticizer) 0.02 parts by weight Dibutyltin bis-acetoacetonate (10% dissolved in solvent naphta 100) 1.50 parts by weight vinyltrimethoxysilane 46.2 parts by weight Precipitation chalk (type: Socal® U1S2) 2.00 parts by weight maleate 1.40 parts by weight Disparlon® NVG8403 S (thixotropic agent from Kusumoto Chem. Ltd.)

    Die Mischung wird 10 Minuten bei einem Druck von 100 mbar dispergiert, wobei die Innentemperatur auf 60°C ansteigt. Anschließend werden 1,5 Gew.-Teile N-Aminoethyl-3-aminopropyl-trimethoxysilan zugegeben und bei einem Druck von 100 mbar durch 10 minütiges Rühren eingearbeitet. Der so hergestellte Dichtstoff zeigt eine ausgezeichnete Standfestigkeit, haftet auf nahezu allen Untergründen und härtet mit einer Hautbildungszeit von 30 Minuten aus.The mixture is dispersed for 10 minutes at a pressure of 100 mbar, the internal temperature rising to 60 ° C. Then be 1.5 parts by weight N-aminoethyl-3-aminopropyltrimethoxysilane added and incorporated at a pressure of 100 mbar by stirring for 10 minutes. The sealant produced in this way shows excellent stability, adheres to almost all substrates and hardens with a skin formation time of 30 minutes.

    Das Produkt wird in eine handelsübliche Kartusche abgefüllt und bei 50°C gelagert. Nach einer Lagerdauer von 90 Tagen läßt sich das Produkt noch problemlos verarbeiten und zeigt unveränderte Produkteigenschaften. The product is filled into a commercially available cartridge and stored at 50 ° C. After a storage period of 90 days, the product can still be processed without any problems and shows unchanged product properties.

    Die folgenden mechanischen Eigenschaften wurden bestimmt: Zugfestigkeit 2,6 N/mm2 (DIN 53504) Reißdehnung 268 % (DIN 53504) Weiterreißwiderstand 5,4 N/mm (DIN 53515) Shore A-Härte 42 The following mechanical properties were determined: tensile strenght 2.6 N / mm 2 (DIN 53504) elongation at break 268% (DIN 53504) Tear strength 5.4 N / mm (DIN 53515) Shore A hardness 42

    Beispiel 2Example 2 Herstellung einer erfindungsgemäßen PolyurethanmasseProduction of a polyurethane composition according to the invention

    In einem handelsüblichen Planetenmischer werden die folgenden Komponenten zu einem gebrauchsfertigen Dichtstoff verarbeitet: 36,0 Gew-Teile Polyurethan A2 12,6 Gew.-Teile Diisoundecylphtalat (Weichmacher) 0,02 Gew.-Teile Dibutylzinn-bis-acetoacetonat (10%ig gelöst in Solventnaphta 100) 2,20 Gew.-Teile Vinyltrimethoxysilan 45,68 Gew.-Teile Fällungskreide (Typ: Socal® U1S2 der Fa. Solvay GmbH) 2,0 Gew.- Teile Maleinsäuredimethylester 1,4 Gew.-Teile Cabosil® TS 720 (pyrogene Kieselsäure der Fa. Cabot GmbH) The following components are processed into a ready-to-use sealant in a commercially available planetary mixer: 36.0 parts by weight Polyurethane A 2 12.6 parts by weight Diisoundecyl phthalate (plasticizer) 0.02 parts by weight Dibutyltin bis-acetoacetonate (10% dissolved in Solventnaphta 100) 2.20 parts by weight vinyltrimethoxysilane 45.68 parts by weight Precipitation chalk (type: Socal® U1S2 from Solvay GmbH) 2.0 parts by weight maleate 1.4 parts by weight Cabosil® TS 720 (fumed silica from Cabot GmbH)

    Die Mischung wird 10 Minuten bei einem Druck von 100 mbar dispergiert, wobei die Innentemperatur auf 60°C ansteigt Anschließend werden 2,1 Gew.-Teile N-Aminoethyl-3-aminopropyl-trimethoxysilan zugegeben und bei einem Druck von 100 mbar durch 10 minütiges Rühren eingearbeitet. The mixture is dispersed for 10 minutes at a pressure of 100 mbar, the internal temperature rising to 60 ° C. Then 2.1 parts by weight N-aminoethyl-3-aminopropyltrimethoxysilane added and incorporated at a pressure of 100 mbar by stirring for 10 minutes.

    Der so hergestellte Dichtstoff zeigt eine ausgezeichnete Standfestigkeit, haftet auf nahezu allen Untergründen und härtet mit einer Hautbildungszeit von 40 Minuten aus.The sealant produced in this way shows excellent stability and adheres almost all substrates and hardens with a skin formation time of 40 minutes out.

    Das Produkt wird in eine handelsübliche Kartusche abgefüllt und bei 50 °C gelagert. Nach einer Lagerdauer von 90 Tagen läßt sich das Produkt noch problemlos verarbeiten und zeigt unveränderte Produkteigenschaften.The product is filled into a commercially available cartridge and stored at 50 ° C. After a storage period of 90 days, the product can still be processed without any problems and shows unchanged product properties.

    Die folgenden mechanischen Eigenschaften wurden bestimmt: Zugfestigkeit 2,8 N/mm2 (DIN 53504) Reißdehnung 290 % (DIN 53504) Weiterreißwiderstand 7,5 N/mm (DIN 53515) Shore A-Härte 46 The following mechanical properties were determined: tensile strenght 2.8 N / mm 2 (DIN 53504) elongation at break 290% (DIN 53504) Tear strength 7.5 N / mm (DIN 53515) Shore A hardness 46

    Beispiel 3Example 3 Nicht erfindungsgemäßes VergleichsbeispielComparative example not according to the invention

    Beispiel 1 wird wiederholt, mit der Änderung daß kein Maleinsäurediethylester zugesetzt wird. Das Produkt wird in eine handelsübliche Kartusche abgefüllt und bei 50°C gelagert. Nach einer Lagerdauer von 60 Tagen läßt sich das Produkt nicht mehr aus der Kartusche auspressen und ist geliert.Example 1 is repeated, with the change that no maleic acid diethyl ester is added becomes. The product is filled into a commercially available cartridge and at 50 ° C stored. After a storage period of 60 days, the product can no longer be used squeeze the cartridge and is gelled.

    Die folgenden mechanischen Eigenschanen wurden bestimmt: Zugfestigkeit 2,5 N/mm2 (DIN 53504) Reißdehnung 235% (DIN 53504) Weiterreißwiderstand 5,6 N/mm (DIN 53515) Shore A-Härte 42 The following mechanical properties were determined: tensile strenght 2.5 N / mm 2 (DIN 53504) elongation at break 235% (DIN 53504) Tear strength 5.6 N / mm (DIN 53515) Shore A hardness 42

    Beispiel 4Example 4 Nicht erfindungsgemäßes VergleichsbeispielComparative example not according to the invention

    Beispiel 2 wird wiederholt, mit der Änderung, daß kein Maleinsäuredimethylester zugesetzt wird. Das Produkt wird in eine handelsübliche Kartusche abgefüllt und bei 50°C gelagert. Nach einer Lagerdauer von 35 Tagen läßt sich das Produkt nicht mehr aus der Kartusche auspressen und ist geliert.Example 2 is repeated with the change that no dimethyl maleate is added. The product is filled into a commercially available cartridge and included in the Stored at 50 ° C. After a storage period of 35 days, the product cannot be Squeeze more out of the cartridge and is gelled.

    Die folgenden mechanischen Eigenschaften wurden bestimmt: Zugfestigkeit 2,8 N/mm2 (DIN 53504) Reißdehnung 250 % (DIN 53504) Weiterreißwiderstand 7,4 N/mm (DIN 53515) Shore A-Härte 46 The following mechanical properties were determined: tensile strenght 2.8 N / mm 2 (DIN 53504) elongation at break 250% (DIN 53504) Tear strength 7.4 N / mm (DIN 53515) Shore A hardness 46

    Beispiel 5Example 5 Herstellung einer erfindungsgemäßen PolyurethanmasseProduction of a polyurethane composition according to the invention

    In einem handelsüblichen Planetenmischer werden die folgenden Komponenten zu einem gebrauchsfertigen Dichtstoff verarbeitet: 36,4 Gew-Teile Polyurethan A1) 12,9 Gew.-Teile Diisoundecylphtalat (Weichmacher) 0,04 Gew.-Teile Dibutylzinn-bis-acetoacetonat (10%ig gelöst in Solventnaphta 100) 1,50 Gew.-Teile Vinyltrimethoxysilan 46,2 Gew.-Teile Fällungskreide (Typ: Socal U1S2) 1,40 Gew.-Teile Disparlon NVG8403 S (Thixotropiermittel der Kusumoto Chem. Ltd.) The following components are processed into a ready-to-use sealant in a commercially available planetary mixer: 36.4 parts by weight Polyurethane A1) 12.9 parts by weight Diisoundecyl phthalate (plasticizer) 0.04 parts by weight Dibutyltin bis-acetoacetonate (10% dissolved in Solventnaphta 100) 1.50 parts by weight vinyltrimethoxysilane 46.2 parts by weight Precipitation chalk (type: Socal U1S2) 1.40 parts by weight Disparlon NVG8403 S (thixotropic agent from Kusumoto Chem. Ltd.)

    Die Mischung wird 10 Minuten bei einem Druck von 100 mbar dispergiert, wobei die Innentemperatur auf 60°C ansteigt. Anschließend werden 2,5 Gew.-Teile N-(3-Trimethoxysilylpropyl)asparaginsäure-diethylester (hergestellt gemäß EP-A 596 360, Bsp. 5) zugegeben und bei einem Druck von 100 mbar durch 10 minütiges Rühren eingearbeitet.The mixture is dispersed for 10 minutes at a pressure of 100 mbar, the internal temperature rising to 60 ° C. Then be 2.5 parts by weight Diethyl N- (3-trimethoxysilylpropyl) aspartate (prepared according to EP-A 596 360, Ex. 5) added and incorporated at a pressure of 100 mbar by stirring for 10 minutes.

    Der so hergestellte Dichtstoff zeigt eine ausgezeichnete Standfestigkeit, haftet auf nahezu allen Untergründen und härtet mit einer Hautbildungszeit von 50 Minuten aus.The sealant produced in this way shows excellent stability and adheres almost all substrates and hardens with a skin formation time of 50 minutes out.

    Das Produkt wird in eine handelsübliche Kartusche abgefüllt und bei 50°C gelagert. Nach einer Lagerdauer von 90 Tagen läßt sich das Produkt noch problemlos verarbeiten und zeigt unveränderte Produkteigenschaften.The product is filled into a commercially available cartridge and stored at 50 ° C. After a storage period of 90 days, the product can still be processed without any problems and shows unchanged product properties.

    Die folgenden mechanischen Eigenschaften wurden bestimmt: Zugfestigkeit 2,5 N/mm2 (DIN 53504) Reißdehnung 310 % (DIN 53504) Weiterreißwiderstand 6,1 N/mm (DIN 53515) Shore A-Härte 39 The following mechanical properties were determined: tensile strenght 2.5 N / mm 2 (DIN 53504) elongation at break 310% (DIN 53504) Tear strength 6.1 N / mm (DIN 53515) Shore A hardness 39

    Claims (6)

    1. Polyurethane compositions which crosslink by way of a silane polycondensation and comprise
      A) at least one alkoxysilane-functional polyurethane containing terminal groups of the general formula (I)
      Figure 00210001
         in which
      R1
      is an organic radical having 1 to 12 carbon atoms,
      n
      is an integer from 2 to 4
      and
      X,Y and
      Z are identical or different organic radicals, with the proviso that at least one of the radicals is an alkoxy group with from 1 to 4 carbon atoms,
      B) at least one basic filler,
      C) at least one reaction product of at least one aminosilane of the general formula (II)
      Figure 00220001
         in which
      R2
      is a hydrogen atom or an aminoethyl group and
         n, X, Y and Z are as defined for formula (I),
         with at least one maleic or fumaric acid (ester) of the general formula (III) R3OOC-CH=CH-COOR3    in which
         R3 is an alkyl group having 1 to 12 carbon atoms,
      E) at least one organometallic compound and
      F) if desired, further auxiliaries.
    2. Polyurethane compositions which crosslink by way of a silane polycondensation according to Claim 1, characterized in that used as component A) is at least one alkoxysilyl-functional polyurethane of the general formula (I)
      Figure 00220002
      in which X, Y and Z are each a methoxy group.
    3. Polyurethane compositions which crosslink by way of a silane polycondensation according to Claim 1 and 2, characterized in that used as component A) is at least one alkoxysilyl-functional polyurethane of the general formula (I)
      Figure 00230001
      in which R1 is a radical of the general formula (IIb)
      Figure 00230002
         where R4 is an alkyl group having 1 to 4 carbon atoms.
    4. Polyurethane compositions which crosslink by way of a silanepolycondensation according to Claim 1, characterized in that used as component C) are aminosilane compounds of the general formula (V)
      Figure 00230003
      in which
      R3
      is a linear or branched aliphatic hydrocarbon radical having not more than 12 carbon atoms, n is 3 and X, Y and Z are methoxy or ethoxy radicals.
    5. Process for preparing condensation-crosslinking polyurethane compositions according to Claim 1, according to which components A), B), E) and, where used, F, are mixed in the absence of moisture and subsequently component C) is added to the mixture.
    6. Use of condensation-crosslinking polyurethane compositions according to Claim 1 as sealant, adhesive or coating material.
    EP00943797A 1999-06-25 2000-06-13 Condensation cross-linking polyurethane materials containing special aminosilanes, a method for the production thereof and their use Expired - Lifetime EP1196469B1 (en)

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    Application Number Priority Date Filing Date Title
    DE19929029 1999-06-25
    DE1999129011 DE19929011A1 (en) 1999-06-25 1999-06-25 Polyurethane composition, useful as sealant, comprises alkoxysilane functionalized polyurethane, product of aminosilane with maleic or fumaric acid ester and organometallic compound.
    DE19929029A DE19929029A1 (en) 1999-06-25 1999-06-25 Novel alkoxysilane group containing piperazinone derivatives are useful as additives for lacquers, coatings, adhesives and sealants, preferably those that are cross-linked via silane polycondensation
    DE19929011 1999-06-25
    PCT/EP2000/005392 WO2001000700A2 (en) 1999-06-25 2000-06-13 Condensation cross-linking polyurethane materials containing special aminosilanes, a method for the production thereof and their use

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